AU2001242510B2

AU2001242510B2 - Etching pastes for inorganic surfaces

Info

Publication number: AU2001242510B2
Application number: AU2001242510A
Authority: AU
Inventors: Lilia Heider; Sylke Klein; Armin Kubelbeck; Werner Stockum; Claudia Zielinski
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2000-04-28
Filing date: 2001-03-23
Publication date: 2006-02-23
Anticipated expiration: 2021-03-23
Also published as: JP2003531807A; US20030160026A1; IL152497A0; KR20030004377A; CA2407530C; CN1426381A; RU2002130248A; PL207872B1; MXPA02010634A; HK1053295A1; CN100343189C; KR100812891B1; TWI243801B; PL358687A1; EP1276701B1; RU2274615C2; AU4251001A; WO2001083391A1; CA2407530A1; EP1276701A1

Description

J

WO 01/83391 PCT/EP01/03317 Etching pastes for inorganic surfaces The present invention relates to novel etching media in the form of printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour for etching inorganic, glass-like amorphous or crystalline surfaces, in particular of glasses or ceramics, preferably on SiO 2 or silicon nitridebased systems, and to the use of these etching media.

The term 'inorganic surfaces' is taken to mean oxidic and nitride-containing compounds of silicon, in particular silicon oxide and silicon nitride surfaces.

Definition of glass: The term 'glass' is per se taken to mean a uniform material, for example quartz glass, window glass or borosilicate glass, and also thin layers of these materials produced on other substrates (for example ceramics, metal sheeting or silicon wafers) by various processes known to the person skilled in the art (CVD, PVD, spin-on, thermal oxidation, inter alia).

The term 'glasses' below is taken to mean silicon oxide- and silicon nitridecontaining materials which exist in the solid amorphous state without the glass components crystallizing out and have a high degree of disorder in the microstructure owing to the lack of a long-range order.

Besides pure SiO 2 glass (quartz glass), all glasses are included (for example doped glasses, such as borosilicate, phosphosilicate and borophosphosilicate glasses, coloured, milk and crystal glasses, optical glasses) which comprise Si02 and other components, in particular elements such as, for example, calcium, sodium, aluminium, lead, lithium, magnesium, barium, potassium, boron, beryllium, phosphorus, gallium, arsenic, antimony, lanthenum, zinc, thorium, copper, chromium, manganese, iron, cobalt, nickel, molybdenum, vanadium, titanium, gold, platinum, palladium, silver, cerium, caesium, niobium, tantalum, zirconium, neodymium and praseodymium, which occur in the glasses or function as doping elements in the glasses in the form of oxides, carbonates, nitrates, phosphates, sulfates and/or halides.

Doped glasses are, for example, borosilicate, phosphosilicate and borophosphosilicate glasses, coloured, milk and crystal glasses and optical glasses.

I J WO 01/83391 PCT/EP01/03317 -2- The silicon nitride may likewise comprise other elements, such as boron, aluminium, gallium, indium, phosphorus, arsenic or antimony.

Definition of silicon oxide- and silicon nitride-based systems: The term 'silicon oxide-based systems' is applied below to all crystalline systems which do not fall under the definition given above for amorphous SiO 2 glasses and are based on silicon dioxide; these can be, in particular, the salts and esters of orthosilicic acid and condensation products thereof generally referred to as silicates by the person skilled in the art and quartz and glass-ceramics.

This definition also covers other silicon oxide- and silicon nitride-based systems, in particular the salts and esters of orthosilicic acid and condensation products thereof. Besides pure SiO 2 (quartz, tridymite and cristobalite), the definition covers all Si02-based systems that are built up from SiO 2 or from 'discrete' and/or linked [SiO 4 tetrahedra, such as, for example, nesosilicates, sorosilicates, cyclosilicates, inosilicates, phyllosilicates and tectosilicates, and other components, in particular elements/ components such as, for example, calcium, sodium, aluminium, lithium, magnesium, barium, potassium, beryllium, scandium, manganese, iron, titanium, zirconium, zinc, cerium, yttrium, oxygen, hydroxyl groups and halides.

The term 'silicon nitride-based systems' is applied below to all crystalline and partially crystalline (usually referred to as microcrystalline) systems which do not fall under the definition given above for amorphous silicon nitride glasses/layers. These include Si 3

N

4 in its a-Si 3

N

4 and P-Si 3

N

4 modifications and all crystalline and partially crystalline SiNx and SiNx:H layers. The crystalline silicon nitride may comprise other elements, such as boron, aluminium, gallium, indium, phosphorus, arsenic and antimony.

1. Etching of structures on glass The use of etchants, i.e. chemically aggressive compounds, causes dissolution of the material subjected to the attack by the etchant. It is not only the first layer of the attack surface but also seen from the attack surface deeper layers that are attacked and removed.

I

WO 01/83391 PCT/EP01/03317 -3- 2. Etching of structures on silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems According to the current state of the art, any desired structures can be etched selectively in silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems or their surfaces or their layers of variable thickness, directly by laser-supported etching methods or, after masking, by wet-chemical methods or by dry-etching methods In the laser-supported etching methods, the laser beam scans the entire etch pattern point for point on the glass, which, in addition to a high degree of precision, also requires considerable adjustment effort and is very timeconsuming.

The wet-chemical and dry etching methods include material-intensive, timeconsuming and expensive process steps: A. masking of the areas not to be etched, for example by: Sphotolithography: production of a negative or positive of the etch structure (depending on the resist), coating of the substrate surface (for example by spin coating with a suitable photoresist), drying of the photoresist, exposure of the coated substrate surface, development, rinsing, if desired drying B. etching of the structures by: dip methods (for example wet etching in wet-chemical banks): dipping of the substrates into the etch bath, etching process, repeated rinsing in H 2 0 cascade basins, drying spin-on or spray methods: the etching solution is applied to a rotating substrate, the etching operation can take place without/with input of energy (for example IR or UV irradiation), and this is followed by rinsing and drying dry-etching methods, such as, for example, plasma etching in expensive vacuum units or etching with reactive gases in flow reactors D. J. Monk, D. S. Soane, R. T. Howe, Thin Solid Films 232 (1993), 1 J. BOhler, Steiner, H. Baltes, J. Micromech. Microeng. 7 (1997), R1 M. K6hler "Atzverfahren fOr die Mikrotechnik" [Etching Methods for Microtechnology], Wiley VCH 1983.

3. Full-area etching of silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems In order to etch silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems and their layers of variable thickness to a certain depth over the entire area, use is predominantly made of wet-etching methods. The silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems and their layers of variable thickness are dipped into etch baths, which usually contain toxic and highly corrosive hydrofluoric acid or another mineral acid as etching component.

The disadvantages of the etching methods described are due to the timeconsuming, material-intensive, expensive process steps which are in some cases complex from a technologically or safety point of view or are carried out batchwise.

The present invention therefore seeks to provide an etching medium which can be employed in a technologically simple etching method with high potential throughputs for inorganic surfaces, in particular for glass and other silicon oxideor silicon nitride-based systems, and their layers of variable thickness, this simple etching method being significantly less expensive than conventional wet and dry etching methods in the liquid or gas phase.

The invention thus relates to printable, homogeneous, particle-free etching pastes which have an advantageous, non-Newtonian flow behaviour, and to the use thereof for etching inorganic surfaces, in particular surfaces of silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems and their layers of variable thickness.

The invention also relates to the use of these homogeneous, particle-free etching pastes which have non-Newtonian flow behaviour in compared with the conventional wet and dry etching methods in the liquid or gas phase less expensive, technologically simple printing/etching methods for glass and for other silicon dioxide- and silicon nitride-based systems which are suitable for high throughputs and can be carried out continuously.

As now claimed, according to one aspect, the present invention provides printable, homogenous, particle-free etching medium having non-Newtonian flow behaviour for etching surfaces of glasses selected from the group consisting of the glasses based on silicon oxide and the glasses based on silicon nitride, wherein the etching medium is an etching paste having non-Newtonian flow behaviour, which comprises a) at least one etching-component selected from the group consisting of the fluorides, bifluorides and tetrafluoroborates for glass surfaces, where the etching component(s) is (are) present in a concentration of from 2 to 20 by weight based on the total amount of the medium, b) solvent c) thickener comprising from 0.5 to 25 by weight, based on the total amount of the etching medium, of cellulose/cellulose derivatives, starch/starch derivatives and/or polymers based on acrylate or functionalized vinyl units, wherein the thickener is not xanthan gum, and d) optionally, organic and/or inorganic acid, and, optionally, e) additives, such as antifoams, thixotropic agents, flow-control agents, deaeration agents and adhesion promoters, is effective even at temperatures of from 15 to 50 OC or is activated, if necessary, by input of energy.

The production, shaping and aftertreatment, such as, for example, grinding, polishing, lapping and heat treatment, of the SiO 2 -based systems are as in the case of the glasses unimportant for the use described in accordance with the invention of printable, homogeneous, particle-free etching pastes having non- Newtonian flow behaviour.

The invention relates both to the etching of SiO 2 or silicon nitride-coated substrates as uniform, full, nonporous and porous solids (for example glass grains and powders, and flat, hollow, mirror or sintered glass), obtained, for example, from glass melts, and also to the etching of nonporous and porous glass layers of variable thickness which have been produced on other substrates (for example on ceramics, metal sheeting or silicon wafers) by various methods known to the person skilled in the art (for example CVD, PVD, spin-on of Si-containing precursors, thermal oxidation The etching pastes are applied in a single process step to the substrate surface to be etched. The surface to be etched can be a surface or part-surface on a homogeneous, solid, porous or nonporous element made from silicon oxide- or silicon nitride-based glass or other silicon oxide- or silicon nitride-based systems (for example the surface of a silicon oxide glass sheet) and/or a surface or partsurface of a porous or nonporous layer of glass or other silicon oxide- or siliconnitride based systems on a support material.

A method with a high degree of automation and high throughput which is suitable for transfer of the etching paste to the substrate surface to be etched uses printing technology. In particular, screen printing, silk-screen printing, pad printing, stamp printing and ink-jet printing methods are printing methods which are known to the person skilled in the art. Manual application is likewise possible.

WO 01/83391 PCT/EP01/03317 -6- Depending on the design of the screen, silk screen, klischee or stamp or the cartridge addressing, it is possible to apply the printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour which are described in accordance with the invention over the entire area or selectively in accordance with the etch structure mask only to the points at which etching is desired. All masking and lithography steps as described under A) are unnecessary. The etching operation can take place with or without input of energy, for example in the form of heat radiation (using IR emitters). After etching is complete, the printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour are rinsed off the etched surface using a suitable solvent or burnt out.

By variation of the following parameters, the etch depth in silicon oxide- and silicon nitride-based glasses or other silicon oxide- and silicon nitride-based systems and their layers of variable thickness, and in the case of selective structure etching, in addition the edge sharpness of the etch structures can be adjusted; concentration and composition of the etching components concentration and composition of the solvents employed concentration and composition of the thickener systems concentration and composition of any acids added concentration and composition of any additives added, such as antifoams, thixotropic agents, flow-control agents, deaeration agents and adhesion promoters viscosity of the printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour which are described in accordance with the invention etching duration with or without input of energy into the inorganic surface printed with the respective printing paste and their layers, and input of energy into the system printed with the etching paste.

WO 01/83391 PCT/EP01/03317 -7- The etching duration can be between a few seconds and several minutes, depending on the application, desired etching depth and/or edge sharpness of the etch structures. In general, an etching duration of between 1 and minutes is set.

The printable, homogeneous, particle-free etching pastes having non- Newtonian flow behaviour which are described in accordance with the invention are compared with liquid, dissolved or gaseous etchants, such as inorganic mineral acids from the group consisting of hydrofluoric acid, fluorides, HF gas and SF 6 advantageously significantly simpler and safer to handle and are significantly more economical with respect to the amount of etchant.

The printable, homogeneous, particle-free etching pastes having non- Newtonian flow behaviour according to the invention have the following composition: a. an etching component for glass or for other SiO 2 -based systems and layers thereof b. solvent c. thickener d. if desired, organic and/or inorganic acid(s) e. if desired, additives, such as antifoams, thixotropic agents, flow-control agents, deaeration agents and adhesion promoters.

The etching action of the printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour which are described in accordance with the invention on surfaces of silicon oxide- and silicon nitridebased glasses and other silicon oxide- and silicon nitride-based systems is based on the use of solutions of fluoride-containing components with or without addition of acid, in particular solutions of fluorides, bifluorides, tetrafluoroborates, such as, for example, ammonium, alkali metal and antimony fluorides, ammonium, alkali metal and calcium bifluorides, alkylated ammonium and potassium tetrafluoroborates, and mixtures thereof. These etching components are effective in the etching pastes even at temperatures 0 WO 01/83391 PCT/EP01/03317 -8in the range from 15 to 50 0 C, in particular at room temperature, and/or are activated by input of energy, for example by thermal radiation by IR emitters (up to about 300*C), UV or laser radiation.

The proportion of the etching components employed is in a concentration range of from 2 to 20% by weight, preferably in the range from 5 to 15% by weight, based on the total weight of the etching paste.

The solvent may form the principal constituent of the etching paste. The proportion can be in the range from 10 to 90% by weight, preferably in the range from 15 to 85% by weight, based on the total weight of the etching paste.

Suitable solvents may be inorganic and/or organic solvents, or mixtures thereof. Suitable solvents, which can be employed in pure form or in corresponding mixtures, may be, depending on the application: water simple or polyhydric alcohols, such as, for example, diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, glycerol, 1,5-pentanediol, 2-ethyl-1-hexanol, or mixtures thereof, ketones, such as, for example, acetophenone, methyl-2-hexanone, 2octanone, 4-hydroxy-4-methyl-2-pentanone or 1-methyl-2-pyrrolidone ethers, such as ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether or dipropylene glycol monomethyl ether carboxylic acid esters, such as [2,2-butoxy(ethoxy)]ethyl acetate esters of carbonic acid, such as propylene carbonate inorganic mineral acids, such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or organic acids which have an alkyl radical chain length of n 1 10, or mixtures thereof. The alkyl radical may be either straight-chain or branched. In particular, organic carboxylic, WO 01/83391 PCT/EP01/03317 -9hydroxycarboxylic and dicarboxylic acids, such as formic acid, acetic acid, lactic acid, oxalic acid or the like, are suitable.

These solvents or mixtures thereof are, inter alia, also suitable for removing the etching medium again after etching is complete and, if desired, cleaning the etched surface.

The viscosity of the printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour which are described in accordance with the invention is achieved by network-forming thickeners which swell in the liquid phase and can be varied depending on the desired area of application. The printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour which are described in accordance with the invention include all etching pastes whose viscosity is not independent of the shear rate, in particular etching pastes having a shear-thinning action. The network produced by thickeners collapses under shear stress. The restoration of the network can take place without time delay (non-Newtonian etching pastes having a plastic or pseudoplastic flow behaviour) or with a time delay (etching pastes having a thixotropic flow behaviour).

The printable, homogeneous, particle-free etching pastes having non- Newtonian flow behaviour are completely homogeneous with addition of thickener. Particulate thickeners, such as, for example, particulate silicone or acrylic resins, are not used.

Possible thickeners are polymers based on the following monomer units: Sglucose units 3-glucosidically linked, i.e. cellulose and/or cellulose derivatives, such as cellulose ethers, in particular ethyl- (for example Aqualon® EC), hydroxylpropyl- (for example Klucel®) and hydroxyethylcellulose (for example Natrosol®), and salts of the glycol acid ether of cellulose, in particular sodium carboxymethylhydroxyethylcellulose (for example Na-

CMHEC)

a-glucosidically linked, i.e. starch andlor starch derivatives, such as oxidized starch, in particular sodium carboxymethylstarch (vivastar® WO 01/83391 PCT/EP01/03317 P0100 or vivastar® P5000), and starch ethers, in particular anionic heteropolysaccharides (Deuteron® VT819 or Deuteron® XG) functionalized methacrylate units, in particular cationic methacrylate/methacrylamide, such as Borchigel® A PK functionalized vinyl units, i.e.

-polyvinyl alcohols of various degree of hydrolysis, in particular Mowiol® 47-88 (partially hydrolysed, i.e. vinyl acetate and vinyl alcohol units) or Mowiol® 56-98 (fully hydrolysed) Spolyvinylpyrolidones (PVP), in particular PVP K-90 or PVP K-120 The thickeners can be employed individually or in combinations with other thickeners.

The proportion of the thickeners that is necessary for specific setting of the viscosity range and basically for the formation of a printable paste is in the range from 0.5 to 25% by weight, preferably from 3 to 20% by weight, based on the total weight of the etching paste.

As already described, the etching pastes according to the invention are also completely homogeneous with addition of thickener. They do not comprise any particulate thickeners, such as, for example, particulate silicone or acrylic resins.

Organic and inorganic acids whose pK, value is between 0 and 5 may have been added to the printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour which are described in accordance with the invention. Inorganic mineral acids, such as, for example, hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid, and also organic acids which have an alkyl radical chain length of n 1 10 improve the etching action of the printable, homogeneous, particle-free etching pastes having non-Newtonian flow behaviour. The alkyl radical of the organic acids may be either straight-chain or branched, with organic carboxylic, hydroxycarboxylic and dicarboxylic acids, such as formic acid, acetic acid, lactic acid and oxalic acid, or others being particularly suitable. The WO 01/83391 PCT/EP01/03317 11 proportion of the acid(s) can be in the range from 0 to 80% by weight, based on the total weight of the etching paste.

Additives having properties which are advantageous for the desired purpose are antifoams, such as, for example, the one available under the trade name TEGO® Foamex N, thixotropic agents, such as BYK® 410, Borchigel® Thixo2, flow-control agents, such as TEGO® Glide ZG 400, deaeration agents, such as TEGO® Airex 985, and adhesion promoters, such as Bayowet® FT 929.

These may have a positive effect on the printability of the etching paste. The proportion of the additives is in the range from 0 to 5% by weight, based on the total weight of the etching paste.

Areas of application for the etching pastes according to the invention are found, for example, in the solar cell industry (photovoltaic components, such as solar cells and photodiodes) the semiconductor industry the glass industry high-performance electronics The novel printable, homogeneous, particle-free etching pastes having non- Newtonian behaviour according to the invention can be employed, in particular, in all cases where full-area and/or structured etching of surfaces of silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems and their layers is desired.

Thus, entire surfaces, but also individual structures selectively can be etched down to the desired depth into uniform, solid, nonporous and porous glasses and other uniform, solid, nonporous and porous silicon oxide- and silicon nitride-based systems, i.e. the etching operation can cover all ranges between microstructural roughening (still transparent glasses with a lightscattering effect) via frosting/matting effects to etching of deep etch WO 01/83391 PCT/EP01/03317 12structures (for example markings, ornaments/patterns). Areas of application are, for example: the production of viewing windows for valves and measuring equipment of all types the production of glass supports for outdoor applications (for example for solar cells and heat collectors) etched glass surfaces in the medical and sanitary sector, and for decorative purposes, including artistic and architectural applications etched glass containers for cosmetic articles, foods and drinks specific partial etching of glasses and other silicon oxide-based systems for marking and labelling purposes, for example for marking/labelling container glass and flat glass specific partial etching of glasses and other silicon oxide-based systems for mineralogical, geological and microstructural studies In particular, screen printing, silk-screen printing, pad printing, stamp printing and ink-jet printing methods are suitable techniques for applying the etching pastes as desired. In general, besides the said printing methods, manual application (for example brush) is also possible.

Besides industrial application, the etching pastes are also suitable for DIY and hobby needs.

The printable, homogeneous, particle-free etching pastes having non- Newtonian flow behaviour which are described in accordance with the invention can be employed in all cases where layers of glasses and other silicon oxide-based and silicon nitride-based systems of variable thickness are to be etched over the entire area and/or in a structured manner. Areas of application are, for example: all etching steps on layers of silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems which WO 01/83391 PCT/EP01/03317 13result in the production of photovoltaic components, such as solar cells, photodiodes and the like, in particular a) the removal of silicon oxide/doped silicon oxide (for example phosphorus glass after n-doping of the solar cell) and silicon nitride layers b) the selective opening of passivation layers of silicon oxide and silicon nitride for the generation of two-stage selective emitters (after opening, re-doping in order to produce n layers) andlor local p back surface fields (BSFs) c) edge etching of silicon oxide- and/or silicon nitride-coated solar-cell panels all etching steps on layers of silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems which result in the production of semiconductor components and circuits and which require the opening of passivation layers of silicon oxide and silicon nitride Sall etching steps on layers of silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems which result in the production of components in high-performance electronics In particular, screen printing, silk-screen printing, pad printing, stamp printing and ink-jet printing methods are suitable techniques for application of the etching pastes as desired. In general, besides the said printing methods, manual application is also possible.

WO 01/83391 PCT/EP01/03317 -14- Examples For better understanding and for clarification, examples are given below which are within the scope of protection of the present invention, but are not suitable for restricting the invention to these examples.

Example 1 21 g of ethylene glycol monobutyl ether 39 g of 35% NH 4

HF

2 solution g of formic acid (98-100%) of PVP K-120 Ethylene glycol monobutyl ether and formic acid are introduced into a PE beaker. An aqueous 35% NH 4

HF

2 solution is then added. PVP K-120 is then added successively with stirring (at least 400 rpm). During the addition and for about 30 minutes thereafter, vigorous stirring must be continued. The transfer into containers takes place after a short standing time. This standing time is necessary so that the bubbles formed in the etching paste are able to dissolve.

This mixture gives an etching paste with which silicon oxide- and silicon nitride-based glasses and other silicon oxide- and silicon nitride-based systems and their layers can be etched specifically down to the desired depth over the entire area or in structures with and/or without input of energy.

The etching rate, determined by photospectrometry, on a thermally generated silicon oxide layer is 120 nm/min in the case of etching over the entire area.

The etching rate, determined by photospectrometry, on a silicon nitride layer generated by means of PE-CVD (refractive index n 1.98) is 70 nm/min in the case of etching over the entire area.

The etching paste obtained has a long shelf life, is easy to handle and is printable. It can be removed from the printed material or from the paste carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for example, using water, or burnt out in an oven.

WO 01/83391 PCT/EP01/03317 Example 2 22 g of triethylene glycol monomethyl ether 43 g of 35% NH 4

HF

2 solution g of deionised water 12 g of PVP K-120 Triethylene glycol monomethyl ether is initially introduced, and all the liquid components are added with stirring as in Example 1. Finally, the thickener PVP K-120 is introduced successively with stirring (at least 400 rpm). During the addition and for about 30 minutes thereafter, vigorous stirring must be continued. The transfer into containers takes place after a short standing time. This standing time is necessary in order that the bubbles formed in the etching paste are able to dissolve.

This mixture gives an etching paste with which silicon oxide- and silicon nitride-based glasses and other SiO 2 and silicon nitride-based systems and their layers can be etched specifically down to the desired depth over the entire area or in structures with and/or without input of energy.

The etching rate, determined by photospectrometry, on a thermally generated silicon oxide layer is 106 nm/min in the case of etching over the entire area.

The etching paste obtained has a long shelf life, is easy to handle and is printable. It can be removed from the printed material or from the paste carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for example, using water or burnt out in an oven.

Example 3 12 g of solid NH 4

HF

2 142 g of lactic acid g of ethylcellulose 36 g of ethylene glycol monobutyl ether The ethylcellulose is stirred successively into the initially introduced ethylene glycol monobutyl ether at 40 0 C in a water bath. The solid NH 4

HF

2 is dissolved in the lactic acid, likewise with stirring, and subsequently added to WO 01/83391 PCT/EP01/03317 -16the ethylcellulose stock paste. The two together are then stirred at 600 rpm for 2 hours.

The etching rate, determined by photospectrometry, on a thermally generated silicon oxide layer is 23 nm/min in the case of etching over the entire area.

The etching paste obtained has a long shelf life, is easy to handle and is printable. It can be removed from the printed material or from the paste carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for example, using acetone or butyl acetate or burnt out in an oven.

Example 4 g of ethylene glycol monobutyl ether g of triethylene glycol monomethyl ether 29 g of propylene carbonate 72 g of formic acid 46 g of 35% NH 4

HF

2 solution 24 g of PVP The solvent mixture and the formic acid are introduced into a PE beaker. An aqueous 35% NH 4

HF

2 solution is then added. PVP K-120 is then added successively with stirring (at least 400 rpm). During the addition and for about minutes thereafter, vigourous stirring must be continued. The transfer into containers takes place after a short standing time. This standing time is necessary so that the bubbles formed in the etching paste are able to dissolve.

-17- The etching rate, determined by photospectrometry, on a thermally generated silicon oxide layer is 67 nm/min in the case of selective etching of structures with a width of about 80 .pm. The etching rate, determined by photo-spectrometry, on a silicon nitride layer generated by means of PE-CVD is 35 nm/min in the case of selective etching of structures with a width of about 100 pm and at an etching temperature of 400C.

The etching paste obtained has a long shelf life, is easy to handle and is printable.

It can be removed from the printed material or from the paste carrier (screen, knife, silk screen, stamp, klischee, cartridge, etc.), for example, using water, or burnt out in an oven.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that the prior art forms part of the common general knowledge in Australia.

Claims

1. Printable, homogenous, particle-free etching medium having non-Newtonian flow behaviour for etching surfaces of glasses selected from the group consisting of the glasses based on silicon oxide and the glasses based on silicon nitride, wherein the etching medium is an etching paste having non- Newtonian flow behaviour, which comprises a) at least one etching-component selected from the group consisting of the fluorides, bifluorides and tetrafluoroborates for glass surfaces, where the etching component(s) is (are) present in a concentration of from 2 to 20 by weight based on the total amount of the medium, b) solvent c) thickener comprising from 0.5 to 25 by weight, based on the total amount of the etching medium, of cellulose/cellulose derivatives, starch/starch derivatives and/or polymers based on acrylate or functionalized vinyl units, wherein the thickener is not xanthan gum, and d) optionally, organic and/or inorganic acid, and, optionally, e) additives, such as antifoams, thixotropic agents, flow-control agents, deaeration agents and adhesion promoters, is effective even at temperatures of from 15 to 50 °C or is activated, if necessary, by input of energy.

2. Etching medium according to Claim 1, for surfaces of glasses comprising elements selected from the group consisting of calcium, sodium, aluminium, lead, lithium, magnesium, barium, potassium, boron, beryllium, phosphorus, gallium, arsenic, antimony, lanthanum, scandium, zinc, thorium, copper, chromium, manganese, iron, cobalt, nickel, molybdenum, vanadium, titanium, gold, platinum, palladium, silver, cerium, caesium, niobium, tantalum, zirconium, yttrium, neodymium and praseodymium.

3. Etching medium according to Claim 1 or 2, characterized in that it comprises, as etching component,

19- at least one fluorine compound selected from the group consisting of the ammonium, alkali metal and antimony fluorides, ammonium, alkali metal and calcium bifluorides, and alkylated ammonium and potassium tetrafluoroborates and optionally, at least one inorganic mineral acid selected from the group consisting of hydrochloric acid, phosphoric acid, sulphuric acid and nitric acid and/or, optionally, at least one organic acid, which may contain a straight-chain or branched alkyl radical having 1 10 carbon atoms, selected from the group consisting of alkylcarboxylic acids, hydrocarboxylic acids and dicarboxylic acids. 4. Etching medium according to Claim 1 or 2, characterized in that it comprises an organic acid selected from the group consisting of formic acid, acetic acid, lactic acid and oxalic acid. Etching medium according to Claim 1 or 2, characterized in that the portion of the organic and/or inorganic acids is in a concentration range from 0 to by weight, based on the total amount of the medium, the added acids each having a pKa value of between 0 and 6. Etching medium according to Claim 1 or 2, characterized in that it comprises, as solvent, water, monohydric or polyhydric alcohols, such as glycerol, 1,2- propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 2-ethyl-I- hexenol, ethylene glycol and dipropylene glycol, and ethers thereof, such as ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropyleneglycol monomethyl ether, and esters, such as [2,2-butoxy(ethoxy)]ethylacetate, esters of carbonic acid, such as propylene carbonate, ketones, such as acetophenone, methyl-2- hexanone, 2-octanone, 4-hydroxy-4-methyl-2-penta none and 1-methyl-2- pyrrolidone, as such or as a mixture, in an amount of from 10 90 by weight, preferably in an amount of from 15 85 by weight, based on the total amount of the medium. 7. Etching medium according to Claim 1 or 2, characterized in that it comprises from 0 5% by weight, based on the total amount, of additives selected from the group consisting of antifoams, thixotropic agents, flow-control agents, deaeration agents and adhesion promoters. 8. Use of an etching medium according to Claim 1 or 2 in an etching method in which it is applied to the surface to be etched and removed again after an exposure time of 1 15 minutes. 9. Use of an etching medium according to Claim 1 or 2 in the photovoltaics, semiconductor technology, high-performance electronics, mineralogy or glass industries and for the production of photodiodes, of viewing windows for valves or measuring equipment, of glass supports for outdoor applications, for the production of etched glass surfaces in the medical, decorative and sanitary sectors, for the production of etched glass containers for cosmetic articles, foods and drinks, for the production of markings or labels on containers and in the production of flat glass. Use of an etching medium according to Claim 1 or 2 in screen printing, silk- screen printing, pad printing, stamp printing, ink-jet printing and manual printing methods. 11. Use of an etching medium according to Claim 1 or 2 for the production of glass supports for solar cells or for thermal collectors. 12. Use of an etching medium according to Claim 1 or 2 for etching Si02- or silicon nitride-containing glasses as uniform, full, nonporous or porous solids or of corresponding nonporous or porous glass layers of variable thickness which have been produced on other substrates. 13. Use of an etching medium according to Claim 1 or 2 for etching uniform, solid, nonporous or porous glasses based on silicon oxide or silicon nitride systems and of variable-thickness layers of such systems. -21- 14. Use of an etching medium according to Claim 1 or 2 for the removal of silicon oxide/doped silicon oxide and silicon nitride layers, for the selective opening of passivation layers of silicon oxide and silicon nitride for the generation of two-stage selective emitters and/or local p back surface fields and for edge etching of silicon oxide- and silicon nitride-coated solar cells. Use of an etching medium according to Claim 1 or 2 for opening passivation layers of silicon oxide and silicon nitride in the process for the production of semiconductor components and their circuits. 16. Use of an etching medium according to Claim 1 or 2 for opening passivation layers of silicon oxide and silicon nitride in the process for the production of components for high-performance elements. 17. Use of an etching medium according to Claim 1 or 2 for mineralogical, geological and microstructural studies. 18. Method for etching inorganic, glass-like, crystalline surfaces, characterized in that an etching medium according to Claim 1 or 2 is applied over the entire area or specifically in accordance with the etch structure mask only to the points at which etching is desired, and, after etching is complete, is rinsed off with a solvent mixture of burnt off in an oven. 19. Method according to Claim 18, characterized in that the etching medium is rinsed off with water after the etching is complete. Etching medium according to Claim 1 or 2, wherein the etching component is present in a concentration of from 5 to 15% by weight based on the total amount of the medium.

21. Etching medium according to Claim 1 or 2, wherein the thickener comprises from 3 20% by weight based on the total amount of the medium of cellulose/cellulose derivates, starch/starch derivates and/or polymers based on acrylate or functionalized vinyl units. -22-

22. Printable, homogenous, particle-free etching medium substantially as hereinbefore described with reference to the examples. DATED THIS 19th day of August, 2005. MERCK PATENT GMBH By Its Patent Attorneys DAVIES COLLISON CAVE